PROCEDE D'HYDROXYCARBONILATION DE DIISOBUTENE CATALYSEE PD : RAPPORT D'ACIDE 3,5,5-TRIMETHYLHEXANOIOEQUE/H2O

PROCESS FOR PD-CATALYZED HYDROXYCARBONYLATION OF DIISOBUTENE: RATIO OF 3,5,5-TRIMETHYLHEXANOIC ACID/H2O

Abrégé français

Il est décrit un procédé pour lhydroxycarbonylation à Pd catalysé de diisobutylène : rapport 3,5,5-acide triméthylhexanoïque-H2O.

Abrégé anglais

Process for Pd-catalyzed hydroxycarbonylation of diisobutene: ratio of 3,5,5-trimethylhexanoic acid/H2O.

Revendications

5
Claims
1. Process comprising the process steps of preparing a reaction mixture,
said reaction
mixture resulting from:
a) an addition of diisobutene,
b) an addition of a compound comprising Pd, wherein the Pd is capable of
forming a
complex,
c) an addition of the ligand L1:
Image
d) an addition of 3,5,5-trimethylhexanoic acid and water, wherein the ratio
based on
the volumes used is in the range from 0.75/1.25 to 1.8/0.2, and
e) a feeding in CO, and
f) heating the reaction mixture such that the diisobutene is converted to the
compound P1:
Image
2. Process according to claim 1,
wherein the compound in process step b) is selected from the group consisting
of:
PdCl2, PdBr2, Pd(acac)2, Pd(dba)2 (dba = dibenzylideneacetone), and
PdCl2(CH3CN)2.
3. Process according to claim 1 or 2,

6
wherein the process further comprises an additional reaction step g) for an
addition
of CF3SO3H to the reaction mixture.
4. Process according to any one of claims 1 to 3,
wherein the reaction mixture is heated to a temperature in the range from
80°C to
160 C in process step f).
5. Process according to any one of claims 1 to 4,
wherein the CO is fed in process step e) such that the reaction proceeds under
a CO
pressure in the range from 20 bar to 60 bar.
6. Process according to any one of claims 1 to 5,
wherein the ratio of 3,5,5-trimethylhexanoic acid/water based on the volumes
used is
in the range from 1.0/1.0 to 1.8/0.2.
7. Process according to any one of claims 1 to 6,
wherein the amount of 3,5,5-trimethylhexanoic acid added per 1 mmol of
diisobutene
is in the range from 0.3 ml to 0.4 ml.

Description

I
Process for Pd-catalyzed hydroxycarbonylation of diisobutene:
ratio of 3,5,5-trimethylhexanoic acid/H20
The invention relates to a process for Pd-catalyzed hydroxycarbonylation of
diisobutene:
ratio of 3,5,5-trimethylhexanoic acid/H20
Carboxylic acids including propionic acid, adipic acid and fatty acids are
used in the
preparation of polymers, pharmaceuticals, solvents and food additives. The
routes leading
to carboxylic acids generally include the oxidation of hydrocarbons, alcohols
or aldehydes,
the oxidative cleavage of olefins by ozonolysis, the hydrolysis of
triglycerides, nitriles, esters
or amides, the carboxylation of Grignard or organolithium reagents, and the
halogenation
and subsequent hydrolysis of methyl ketones in the haloform reaction.
The hydroxycarboxylation of olefins is a highly promising and environmentally-
friendly
method for obtaining carboxylic acids. Acetic acid is produced by
carbonylation of methanol,
which is carried out with iodide. In the Koch reaction, the addition of water
and carbon
monoxide to alkenes is catalyzed by strong bases. This method is effective
with alkenes
that form secondary and tertiary carbocations, e.g. isobutylene to pivalic
acid.
Hydroxycarboxylation occurring with the simultaneous addition of CO and H20 to

alkenes/alkynes provides a direct and convenient method for synthesizing
carboxylic acids.
The object of the invention was to provide a process affording good conversion
in the Pd-
catalyzed hydroxycarbonylation of diisobutene (DIBN).
The object is achieved by a process comprising the process steps of preparing
a reaction
mixture, said reaction mixture resulting from:
a) an addition of diisobutene,
b) an addition of a compound comprising Pd, wherein the Pd is capable of
forming a
complex,
c) an addition of a ligand Ll:
Date Recue/Date Received 2020-06-10

2
Fe
SCLP¨P
Li
d) an addition of 3,5,5-trimethylhexanoic acid and water, wherein the ratio
based on the
volumes used is in the range from 0.75/1.25 to 1.8/0.2, and
e) a feeding in CO; and
f) heating the reaction mixture such that the diisobutene is converted to the
compound P1:
COOH
(P1).
In one variant of the process, the compound in process step b) is selected
from the group
consisting of PdC12, PdBr2, Pd(acac)2, Pd(dba)2 (dba = dibenzylideneacetone),
and
PdC12(CH3CN)2.
In one variant of the process, the compound in process step b) is Pd(acac)2.
In one variant of the process, the process further comprises an additional
reaction step g for
an addition of CF3S03H to the reaction mixture.
In one variant of the process, the reaction mixture is heated to a temperature
in the range
from 80 C to 160 C in process step f),
preferably to a temperature in the range from 100 C to 140 C.
In one variant of the process, the CO is fed in process step e) such that the
reaction
proceeds under a CO pressure in the range from 20 bar to 60 bar,
preferably in the range from 30 bar to 50 bar.
In one variant of the process, the ratio of 3,5,5-trimethylhexanoic acid/water
based on the
volumes used is in the range from 1.0/1.0 to 1.8/0.2.
In one variant of the process, the amount of
Date Recue/Date Received 2020-06-10

3
3,5,5-trimethylhexanoic acid added per 1 mmol of diisobutene is in the range
from 0.3 ml
to 0.4 ml.
The invention is elucidated in more detail by means of working examples below.
Pd(acac)21L1/CF3503H COOH/./
(0.25/1.0/7.5 mol%)
DIBN ___________________________________________________ Fie
4.0 mmol CO (40 bar), 3,5,5-trimethylhexanoic acid
H20, 120 C, 20 h
L1 ,
A 4 mL vial was charged with [Pd(acac)2] (3.05 mg, 0.25 mol%), L1 (20.64 mg,
1.0 mol%)
and oven dried stirring bar. The vial was then sealed with septa (PTFE-coated
styrene-
butadiene rubber) and a phenol resin cap. The vial was evacuated and refilled
with argon
three times. H20 (0.5 ml), 3,5,5-trimethylhexanoic acid (1.5 ml), diisobutene
(DIBN) (4.0
mmol) and CF3S03
(7.5 mol%) were added to the vial by syringe. The vial was placed in an alloy
plate, which
was transferred to an autoclave (300 ml) of the 4560 series from Parr
Instruments under
argon atmosphere. After flushing the autoclave three times with CO, the
pressure of CO
was increased to 40 bar at room temperature. The reaction was conducted at 120
C for
h. On conclusion of the reaction, the autoclave was cooled down to room
temperature
and cautiously decompressed. Isooctane (100 pl) was then added as internal
standard.
Conversion was measured by GC analysis.
The experiment described above was repeated with variation of the ratio of
3,5,5-trimethylhexanoic acid/water. All other parameters were maintained.
CA 3028184 2018-12-19

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The results are compiled in the following table.
Entry 3,5,5-Trimethylhexanoic acid/water (mL/mL) Conversion ( % )
1 0/2 25
2 0.2/1.8 45
3 0.5/1.5 49
4 1.0/1.0 84
1.5/0.5 87
6 1.8/0.2 72
CA 3028184 2018-12-19

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